We use Brownian dynamics (BD) simulations and single molecule experiments to investigate the influence of topological constraints and hydrodynamic interactions on the dynamics and rheology of solutions of ring-linear polymer blends at the overlap concentration. We find agreement between simulation and experiment in which rings in solution blends exhibit large conformational fluctuations. A subpopulation of rings shows extension overshoots in the startup of the flow, and other populations display tumbling and tank-treading at the steady state. Ring polymer fluctuations increase with the blend fraction of linear polymers and are peaked at a ring Weissenberg number . On the contrary, linear and ring polymers in pure solutions show a peak in fluctuations at the critical coil-stretch Weissenberg number . BD simulations show that extension overshoots on the startup of the flow are due to flow-induced intermolecular ring-linear polymer hooks, whereas fluctuations at the steady state are dominated by intermolecular hydrodynamic interactions (HIs). This is supported by simulations of bidisperse linear polymer solution blends, which show similar trends in conformational dynamics between rings and linear polymers with a matched contour length. Compared to BD simulations, single molecule experiments show quantitatively larger fluctuations, which could arise because experiments are performed on higher molecular weight polymers with stronger topological constraints. To this end, we have advanced the understanding of the effects of topological interactions and intermolecular HIs on the dynamics of semidilute ring-linear polymer blend solutions.
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July 2021
Research Article|
July 01 2021
Dynamics and rheology of ring-linear blend semidilute solutions in extensional flow. Part I: Modeling and molecular simulations Available to Purchase
Special Collection:
Ring Polymers
Charles D. Young
;
Charles D. Young
1
Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign
, Urbana, Illinois 618012
Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign
, Urbana, Illinois 61801
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Yuecheng Zhou
;
Yuecheng Zhou
a)
2
Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign
, Urbana, Illinois 618013
Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign
, Urbana, Illinois 61801
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Charles M. Schroeder;
Charles M. Schroeder
1
Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign
, Urbana, Illinois 618012
Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign
, Urbana, Illinois 618013
Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign
, Urbana, Illinois 61801
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Charles E. Sing
Charles E. Sing
b)
1
Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign
, Urbana, Illinois 618012
Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign
, Urbana, Illinois 61801b)Author to whom correspondence should be addressed; electronic mail: [email protected]
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Charles D. Young
1,2
Yuecheng Zhou
2,3,a)
Charles M. Schroeder
1,2,3
Charles E. Sing
1,2,b)
1
Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign
, Urbana, Illinois 61801
2
Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign
, Urbana, Illinois 61801
3
Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign
, Urbana, Illinois 61801a)
Current address: Department of Chemistry, Stanford University, Stanford, California 94305, USA.
b)Author to whom correspondence should be addressed; electronic mail: [email protected]
Note: This paper is part of the special issue on Ring Polymers.
Citation
Charles D. Young, Yuecheng Zhou, Charles M. Schroeder, Charles E. Sing; Dynamics and rheology of ring-linear blend semidilute solutions in extensional flow. Part I: Modeling and molecular simulations. J. Rheol. 1 July 2021; 65 (4): 757–777. https://doi.org/10.1122/8.0000221
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